JP5556138B2 - Aqueous emulsion - Google Patents

Description

  The present invention relates to an aqueous emulsion and the like.

Polypropylene is used for, for example, automobile parts such as bumpers because of its excellent processability and strength. A paint is usually applied to an automobile part for decoration or the like.
Since it is difficult for other materials such as paint to adhere to the surface of polypropylene, it is common practice to apply paint after applying chlorinated polyolefin with excellent adhesion to polypropylene to polypropylene. (For example, Patent Document 1).

JP 5-7832 A ([Claims])

  Since the chlorinated polyolefin contains chlorine atoms, there is a problem that when the polypropylene coated with the chlorinated polyolefin is burned, hydrochloric acid gas is generated and the disposal of the polypropylene is complicated. There is a demand for a material excellent in adhesiveness to polypropylene.

Under such circumstances, as a result of intensive studies, the present inventors have reached the inventions shown in [1] to [12] below.
[1] An aqueous emulsion containing the following (A), (B) and (C).
(A) an acrylic copolymer containing a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester, and a structural unit derived from ethylene and / or a structural unit derived from propylene, or , Modified acrylic copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acid to the copolymer (B) ionic emulsifier (C) water [2] (A) acrylic copolymer Content of the structural unit derived from an acrylate ester or the structural unit derived from a methacrylic acid ester in a polymer is 5 to 40 weight% or less, The aqueous emulsion of the preceding clause [1] characterized by the above-mentioned.
[3] The aqueous emulsion according to [1] or [2] above, wherein the ionic emulsifier used in (B) is an anionic emulsifier.
[4] The anionic emulsifier is a water-soluble acrylic resin containing a structural unit derived from an α, β-unsaturated carboxylic acid and a structural unit derived from an α, β-unsaturated carboxylic acid ester. The aqueous emulsion according to [3] above.

[5] A method for producing an aqueous emulsion comprising a kneading step of kneading the following (A) and (B), and a step of dispersing the kneaded product obtained in the kneading step in the following (C).
(A) an acrylic copolymer containing a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester, and a structural unit derived from ethylene and / or a structural unit derived from propylene, or A modified acrylic copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the copolymer (B) Ionic emulsifier (C) Water [6] (A) and (B) are kneaded The manufacturing method according to [5], wherein the kneading step is performed while applying a shear stress.

[7] Adhering layer made of at least one material selected from the group consisting of woody materials, cellulosic materials, plastic materials, ceramic materials and metal materials, and any one of [1] to [4] above A laminate having a layer derived from the aqueous emulsion described.
[8] The laminate according to [7] above, wherein the adherend is a polyolefin.

[9] Any one of [1] to [4] above, on an adherend comprising at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material. A first step of applying the aqueous emulsion described above to obtain a coated product having the adherent layer and a layer containing the aqueous emulsion;
The manufacturing method of a laminated body characterized by including the 2nd process of drying the coated article obtained at the 1st process, and obtaining the laminated body which has the said adherence layer and the layer derived from an aqueous emulsion.

[10] A method for forming a coating film comprising a step of applying the aqueous emulsion according to any one of [1] to [4] to the surface of the adherend layer.

[11] Use of the aqueous emulsion according to any one of [1] to [4] above for forming a coating film.

[12] A cured product obtained by drying the aqueous emulsion according to any one of [1] to [4].

  The aqueous emulsion of the present invention is excellent in adhesiveness with polypropylene.

(A) used in the present invention includes a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester, and a structural unit derived from ethylene and / or a structural unit derived from propylene. An acrylic copolymer (hereinafter sometimes referred to as “polymer (A-a)”), or
A modified acrylic copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the polymer (Aa) (hereinafter sometimes referred to as “polymer (Ab)”). . Hereinafter, the polymer (Aa) and the polymer (Ab) may be collectively referred to as “polymer (A)”.

In the polymer (A), examples of the structural unit derived from the acrylate ester and / or the structural unit derived from the methacrylic acid ester include the following formula X-OH:
(In the formula, X represents an alkyl group having 2 to 10 carbon atoms having an epoxy group, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a hydroxyl group.)
The ester etc. which consist of the alcohol shown by and acrylic acid and / or methacrylic acid can be mentioned.

  Examples of the alkyl group having 2 to 10 carbon atoms having an epoxy group include 1,2-epoxyethyl group, 1,2-epoxypropyl group, 1,2-epoxybutyl group, 1,2-epoxypentyl group, 1 1,2-epoxyhexyl group, 1,2-epoxyoctyl group, 1,2-epoxydecyl group, and the like, preferably 1,2-epoxyethyl group, 1,2-epoxypropyl group.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, amyl group, 2-ethylhexyl group, nonyl group and decanyl group. , A cyclohexyl group, and the like, preferably a methyl group and an ethyl group.

  Examples of the alkyl group having 1 to 10 carbon atoms having a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyoctyl group, and a hydroxydecyl group. Preferably, a hydroxymethyl group and a hydroxyethyl group are mentioned.

Content of the structural unit derived from the acrylate ester and / or the structural unit derived from the methacrylic acid ester in the polymer (Aa) is based on all the structural units constituting the polymer (Aa). The amount is usually 5 to 40% by weight, preferably 5 to 35% by weight, particularly preferably 5 to 30% by weight.
It is preferable that the content of the structural unit derived from the acrylate ester and / or the structural unit derived from the methacrylic acid ester is 40% by weight or less because the adhesiveness of the obtained adhesive tends to be improved.
The content of the structural unit derived from the acrylate ester and / or the structural unit derived from the methacrylic acid ester can be determined using a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

  In the polymer (Aa), the total content of a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester and a structural unit derived from ethylene and / or a structural unit derived from propylene The amount is usually 95 to 60% by weight, preferably 95 to 65% by weight, more preferably 95 to 70% by weight, based on all the structural units constituting the polymer (Aa).

(式中、Ｒ’、Ｒ”は、それぞれ独立に、炭素数１〜１８の直鎖状、分枝状あるいは環状のアルキル基、またはハロゲン原子を表す。)
で示されるビニリデン化合物、ジエン化合物、ハロゲン化ビニル、アルキル酸ビニル、ビニルエーテル類、アクリロニトリル類、後述するα，β−不飽和カルボン酸、後述するα，β−不飽和カルボン酸エステル、後述するα，β−不飽和カルボン酸無水物等が挙げられる。 The polymer (Aa) may further be copolymerized with a monomer capable of addition polymerization.
Here, the addition-polymerizable monomer is a monomer excluding acrylic acid ester, methacrylic acid ester, ethylene and propylene, and is a monomer capable of addition polymerization with acrylic acid ester, methacrylic acid ester, ethylene and propylene. The carbon number of the monomer is usually about 3-20.
Specific examples of the monomer capable of addition polymerization include cycloolefin, the following general formula (II)

(In the formula, R ′ and R ″ each independently represent a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a halogen atom.)
Vinylidene compounds, diene compounds, vinyl halides, vinyl alkylates, vinyl ethers, acrylonitriles, α, β-unsaturated carboxylic acids described later, α, β-unsaturated carboxylic esters described later, α, described later (beta) -unsaturated carboxylic acid anhydride etc. are mentioned.

  Examples of the cycloolefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, and 5-ethyl-2-norbornene. 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopenta Decene, 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxy Carbonyl-2-norbornene 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyl-2-tetracyclododecene, 8-methyl-8-methoxycarbonyl -2-tetracyclododecene, 8-cyano-2-tetracyclododecene, and the like. More preferred cycloolefins are cyclopentene, cyclohexene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricyclo Undecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl 2-norbornene and 5-cyano-2-norbornene, preferably 2-norbornene and 2-tetracyclododecene.

  Examples of the vinylidene compound include isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, 2-methyl-1-octene, 2 , 3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1-heptene, 2,3-dimethyl-1-octene, 2 , 4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene, vinylidene chloride and the like. Preferred vinylidene compounds are isobutene, 2,3-dimethyl-1-butene and 2,4,4-trimethyl-1-pentene.

  Examples of the diene compound include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, and 2,5-norbornadiene. , Dicyclopentadiene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene and the like. Preferred diene compounds are 1,4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene. is there.

Examples of vinyl alkylates include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and n-butyl vinyl ether.
Examples of the vinyl halide include vinyl chloride, and examples of the acrylonitrile include acrylonitrile and methacrylonitrile.

  The content of the structural unit derived from the addition-polymerizable monomer in the polymer (Aa) is usually in a range where the adhesiveness of the resulting aqueous emulsion is not impaired, and the specific content is determined by the polymer ( Usually, about 5% by weight or less with respect to all the structural units constituting Aa), preferably not containing substantially any structural unit derived from an addition-polymerizable monomer, specifically 1 The content is not more than wt%.

  As a manufacturing method of a polymer (Aa), a solution polymerization method, a high pressure polymerization method, etc. are mentioned, for example. Among them, it is preferable to produce the same according to the methods described in JP 2006-233059 A, JP 2007-84743 A, and the like.

The molecular weight distribution (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) of the polymer (Aa) is usually about 1.5 to 10.0, preferably 1.5 to 7. About 0, more preferably about 1.5 to 5.0. It is preferable that the molecular weight distribution of the polymer (Aa) is 1.5 or more and 10.0 or less because the mechanical strength and transparency of the resulting polymer (A) tend to be improved.
Moreover, the weight average molecular weight (Mw) of a polymer (Aa) is about 5,000-1,000,000 normally, and from a viewpoint of mechanical strength, Preferably it is about 10,000-500,000. More preferably, it is about 15,000 to 400,000. The polymer (A-1) preferably has a weight average molecular weight of 5,000 or more because the mechanical strength of the resulting polymer (A) tends to be improved, and is 1,000,000 or less. This is preferable because the fluidity of the resulting polymer (A) tends to be improved.
The molecular weight distribution of the polymer (A-a) can be determined using gel permeation chromatograph (GPC) according to the method specifically described in Examples below.

  The intrinsic viscosity [η] of the polymer (Aa) is usually about 0.25 to 10 dl / g, and preferably about 0.3 to 3 dl / g from the viewpoint of mechanical strength.

The value of the melt flow rate (MFR) of the polymer (Aa) is 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210. If it measures below, it is 0.1-300 normally, Preferably it is 0.5-300, More preferably, it is 1-220. In particular, from the viewpoint of film forming property, it is preferably 5 to 300, more preferably 10 to 220.
In addition, MFR of a polymer (Aa) changes the usage-amount of molecular weight modifiers, such as hydrogen, polymerization temperature, etc. in the copolymerization of acrylic acid ester and / or methacrylic acid ester, and ethylene and / or propylene. By doing so, it can be adjusted.

The polymer (Ab) is a polymer obtained by graft polymerization of an α, β-unsaturated carboxylic acid anhydride to the polymer (Aa) thus obtained.
The graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride with respect to 100 parts by weight of the polymer (Ab) is usually 0.01 to 20 with respect to 100% by weight of the resulting polymer (Ab). It is about wt%, preferably about 0.05 to 10 wt%, more preferably about 0.1 to 5 wt%.
When the graft polymerization amount of the α, β-unsaturated carboxylic acid anhydride is 0.01% by weight or more, the adhesive force of the polymer (Ab) tends to be improved, and preferably 20% by weight or less. When it exists, it exists in the tendency for the thermal stability of a polymer (Ab) to improve, and it is preferable.

Examples of the α, β-unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic acid anhydride, methyl nadic anhydride, and hymic anhydride. Further, the above α, β-unsaturated carboxylic acid anhydride may be used in combination.
As the α, β-unsaturated carboxylic acid anhydride, maleic anhydride is preferable.

As a method for producing the polymer (Ab), for example, a method in which the polymer (Aa) is melted and then α, β-unsaturated carboxylic acid anhydride is added to perform graft polymerization, or a polymer ( Examples include a method in which Aa) is dissolved in a solvent such as toluene and xylene, and then α, β-unsaturated carboxylic acid anhydride is added and graft polymerization is performed.
After the polymer (Aa) is melted, α, β-unsaturated carboxylic acid anhydride is added and graft polymerization is performed by melt-kneading using an extruder, so that resins or resins and solids are solidified. Alternatively, it is preferable because various known methods for mixing liquid additives can be employed. More preferable examples include a method in which all or some of the components are combined and mixed separately with a Henschel mixer, a ribbon blender, a blender or the like to form a uniform mixture, and then the mixture is melt-kneaded. it can. As the melt-kneading means, conventionally known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed. Preferably, from the viewpoint that continuous production is possible and productivity is improved, an olefin copolymer, an unsaturated carboxylic acid, and a radical initiator that are sufficiently premixed in advance using a single or twin screw extruder are added. This is a method of carrying out kneading by supplying from the supply port of the extruder. The temperature of the portion where the melt kneading of the extruder is carried out (for example, the cylinder temperature in the case of an extruder) is usually 50 to 300 ° C, preferably 80 to 270 ° C. When the temperature is 50 ° C. or higher, the graft amount tends to be improved, and when the temperature is 300 ° C. or lower, the decomposition of the polymer (Aa) tends to be suppressed. The temperature of the portion of the extruder where the melt kneading is performed is preferably set so that the melt kneading is divided into two stages, the first half and the second half, and the temperature in the second half is higher than the first half. The melt kneading time is usually 0.1 to 30 minutes, preferably 0.1 to 5 minutes. If the melt-kneading time is 0.1 minutes or more, the graft amount tends to be improved, and if the melt-kneading time is 30 minutes or less, the decomposition of the polymer (Aa) tends to be suppressed. To preferred.

In order to graft polymerize the α, β-unsaturated carboxylic acid anhydride to the polymer (Aa), the polymerization is usually carried out in the presence of a radical initiator.
The addition amount of the radical initiator is usually 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer (Aa). The amount added is preferably 0.01 parts by weight or more because the amount of grafting to the polymer (Aa) tends to increase and the adhesive strength tends to improve, and the amount added is preferably 10 parts by weight or less. This is preferable because unreacted radical initiator in the modified product is reduced and the adhesive strength tends to be improved.
The radical initiator is usually an organic peroxide, preferably an organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute. When the decomposition temperature is 50 ° C. or higher, the graft amount tends to be improved, and when the decomposition temperature is 210 ° C. or lower, the decomposition of the polymer (Aa) tends to be reduced. Further, these organic peroxides preferably decompose and generate radicals, and then have an action of extracting protons from the polymer (Aa).

Examples of the organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and percarbonate compounds. . Specifically, dicetyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate Bonate, t-butyl peroxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethyl butyl neodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, 1,1 bis (t-butylper Oxy) cyclohexane, 2,2bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy Acetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-beroxy) valerate, di-t-butylberoxyisophthalate, dic Milperoxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t -Butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroper And oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like. A decomposition temperature of 50 to 210 ° C. is preferable because the graft amount is improved.
Among these organic peroxides, preferred are dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds, and alkyl perester compounds. The addition amount of the organic oxide is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the polymer (Aa).

  The structural unit derived from the α, β-unsaturated carboxylic acid anhydride contained in the polymer (Ab) thus obtained was a ring-opened one even if the acid anhydride group was closed. The ring-closed one and the ring-opened one may be contained.

The molecular weight distribution (Mw / Mn) of the polymer (Ab) is usually 1.5 to 10, preferably 1.5 to 7, and more preferably 1.5 to 5. A molecular weight distribution of 10 or less is preferred because the adhesion of the polymer (A) tends to be improved.
The molecular weight distribution of the polymer (Ab) can be measured in the same manner as the molecular weight distribution of the olefin copolymer.

  The intrinsic viscosity [η] of the polymer (Ab) is usually about 0.25 to 10 dl / g, and preferably about 0.3 to 3 dl / g from the viewpoint of mechanical strength.

The value of the melt flow rate (MFR) of the polymer (Ab) is 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210. If it measures below, it is 10-300 normally, Preferably it is 130-300, More preferably, it is 130-220. In particular, from the viewpoint of dispersibility, it is preferably 20 to 300, more preferably 20 to 250. More preferably, it is 30-230, More preferably, it is 50-210, Most preferably, it is 60-200.
The MFR of the polymer (Ab) is controlled by the reaction temperature at the time of crosslinking in the presence of a radical initiator or graft polymerization with an α, β-unsaturated carboxylic acid anhydride and a radical initiator, It can be carried out depending on conditions such as the type and amount of the radical initiator. In general, when the polymer (Ab) is an ethylene-based polymer, if the amount of the radical initiator is large, the MFR decreases, and when the polymer (A-b) is a polypropylene-based polymer, the radical initiation If the amount of the agent is small, the MFR tends to be small, but the MFR can be controlled by controlling the type of radical initiator and the temperature condition.

(B) is an ionic emulsifier, and may hereinafter be referred to as an emulsifier (B).
Here, examples of the ionic emulsifier include amphoteric emulsifiers, cationic emulsifiers, and anionic emulsifiers, and these can be used alone or in combination.
The emulsifier (B) can also be used in an aqueous solution state. As the emulsifier (B), an anionic emulsifier is preferable.

  Examples of the amphoteric emulsifier include laurylamidopropylacetic acid betaine, laurylaminoacetic acid betaine, and the like.

Examples of the cationic emulsifier include alkyltrimethylammonium salts and dialkyldimethylammonium salts.
Examples of the alkyltrimethylammonium salt include coconut alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, hebenyltrimethylammonium chloride and the like.
Examples of the dialkyldimethylammonium salt include didecyldimethylammonium chloride, dicocoyldimethylammonium chloride, and dioleyldimethylammonium chloride.

Examples of the anionic emulsifier include monoalkyl sulfonate, alkyl polyoxyethylene sulfonate, monoalkyl benzene sulfonate, and monoalkyl phosphate.
Examples of monoalkyl sulfonates include sodium octyl sulfonate, sodium lauryl sulfonate, sodium pentadecyl sulfonate, sodium myristyl sulfonate, sodium stearyl sulfonate, and the like.
Examples of alkyl polyoxyethylene sulfonates include sodium octyl polyoxyethylene sulfonate, sodium lauryl polyoxyethylene sulfonate, sodium pentadecyl polyoxyethylene sulfonate, sodium myristyl polyoxyethylene sulfonate, stearyl polyoxyethylene sulfone. Examples include sodium acid.
Examples of monoalkylbenzene sulfonates include sodium octyl benzene sulfonate, sodium lauryl benzene sulfonate, sodium pentadecyl benzene sulfonate, sodium myristyl benzene sulfonate, sodium stearyl benzene sulfonate, and the like.
Examples of monoalkyl phosphates include sodium monooctyl phosphate, sodium monolauryl phosphate, sodium monopentadecyl phosphate, sodium monomyristyl phosphate, sodium monostearyl phosphate, and the like.

Examples of the anionic emulsifier include water-soluble acrylic resins containing a structural unit derived from an α, β-unsaturated carboxylic acid and a structural unit derived from an α, β-unsaturated carboxylic acid ester. As the anionic emulsifier, such a water-soluble acrylic resin is preferable. Hereinafter, it may be simply referred to as “water-soluble acrylic resin”.
Here, as the α, β-unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid, methyl nadic acid, highmic acid, Examples include angelic acid, tetrahydrophthalic acid, sorbic acid, and mesaconic acid.
As the α, β-unsaturated carboxylic acid, plural kinds of α, β-unsaturated carboxylic acids may be used.
As the α, β-unsaturated carboxylic acid, acrylic acid and methacrylic acid are particularly preferable.

  The α, β-unsaturated carboxylic acid ester is an ester of α, β-unsaturated carboxylic acid, and is obtained from, for example, an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid. α, β-unsaturated carboxylic acid ester, α, β-unsaturated carboxylic acid ester obtained from aliphatic alcohol having 1 to 10 carbon atoms having amino group and α, β-unsaturated carboxylic acid, carbon having hydroxyl group Α, β-unsaturated carboxylic acid ester obtained from aliphatic alcohol of number 1 to 10 and α, β-unsaturated carboxylic acid, C 1-10 aliphatic alcohol having carboxylic acid group and α, β- And α, β-unsaturated carboxylic acid esters obtained from unsaturated carboxylic acids.

  Here, examples of the α, β-unsaturated carboxylic acid constituting the α, β-unsaturated carboxylic acid ester include those similar to the α, β-unsaturated carboxylic acid, and particularly acrylic acid and methacrylic acid. Is preferred.

Examples of the aliphatic alcohol having 1 to 20 carbon atoms include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, t-butyl alcohol, amyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, deca alcohol. Nyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, cyclohexyl alcohol and the like can be mentioned.
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, and acrylic acid. Butyl, amyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decanyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Examples include amyl methacrylate, ethyl hexyl methacrylate, nonyl methacrylate, decanyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and the like. Two or more α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 20 carbon atoms and the α, β-unsaturated carboxylic acid may be used in combination.

Examples of the aliphatic alcohol having 1 to 10 carbon atoms having an amino group include an amino group (—NH ₂ ) and an alkylamino group (—NHR ² and R ² are alkyl having 1 to 10 carbon atoms) on the hydrogen atom of the aliphatic alcohol. Group) or a dialkylamino group (—NR ³ R ⁴ , R ³ and R ⁴ each represent an aliphatic alcohol having 1 to 10 carbon atoms, and R ³ and R ⁴ may be the same or different. ) Means a substituted group. Specifically, aminoalkyl alcohols such as aminomethyl alcohol, aminoethyl alcohol, aminopropyl alcohol; for example, 2- (N-methylamino) ethyl alcohol, 2- (N-ethylamino) ethyl alcohol, 2- (N -Isopropylamino) ethyl alcohol, 3-methylaminopropyl alcohol, 2- (Nn-propylamino) ethyl alcohol, 2- (Nn-butylamino) ethyl alcohol, 2- (N-isobutylamino) ethyl alcohol Alkylaminoalkyl alcohols such as 2- (N-sec-butylamino) ethyl alcohol and 2- (Nt-butylamino) ethyl alcohol; for example, 2- (N, N-dimethylamino) ethyl alcohol, 2- (N-methyl-N-ethylamino) ethyl alcohol And dialkylaminoalkyl alcohols such as 2- (N, N-diethylamino) ethyl alcohol, 3- (N, N-dimethylamino) propyl alcohol and 3- (N, N-diethylamino) propyl alcohol; .
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 10 carbon atoms and an α, β-unsaturated carboxylic acid include N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N-methyl-N-ethylaminoethyl acrylate, N-methyl-N-ethylaminoethyl methacrylate, etc. N, N-dimethylaminoethyl methacrylate is preferred. Two or more kinds of α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 10 carbon atoms having an amino group and the α, β-unsaturated carboxylic acid may be used in combination.

The C1-C10 aliphatic alcohol having a hydroxyl group means a group in which a hydroxyl group is substituted on a hydrogen atom of the aliphatic alcohol. Specific examples include hydroxymethyl alcohol, hydroxyethyl alcohol, hydroxypropyl alcohol, hydroxybutyl alcohol, hydroxypentyl alcohol, hydroxyhexyl alcohol and the like.
Examples of the α, β-unsaturated carboxylic acid ester obtained from a C1-C10 aliphatic alcohol having a hydroxyl group and an α, β-unsaturated carboxylic acid include, for example, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate , Hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, hydroxyhexyl methacrylate, and the like. Two or more α, β-unsaturated carboxylic acid esters obtained from the aliphatic alcohol having 1 to 10 carbon atoms having a hydroxyl group and the α, β-unsaturated carboxylic acid may be used in combination.

As a C1-C10 aliphatic alcohol which has a carboxylic acid group, the carboxylic acid group is substituted by the hydrogen atom of the said aliphatic alcohol. Here, the carboxylic acid group represents an organic group having a carboxy group, and examples thereof include a carboxymethyl group, a 1,2-dicarboxyethyl group, a 2-carboxyphenyl group, and a 2,3-dicarboxyphenyl group. It is done.
Examples of the α, β-unsaturated carboxylic acid ester obtained from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid include 2-acryloyloxyethyl succinic acid, 2 -Acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, etc. are mentioned. Two or more kinds of α, β-unsaturated carboxylic acid esters obtained from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an α, β-unsaturated carboxylic acid may be used in combination.

The content of the structural unit derived from the α, β-unsaturated carboxylic acid in the water-soluble acrylic resin is usually 5 to 95 mol% with respect to all the structural units constituting the water-soluble acrylic resin, preferably Is 5 to 80 mol%.
The content of the structural unit derived from the α, β-unsaturated carboxylic acid ester in the water-soluble acrylic resin is usually 5 to 95 mol% with respect to all the structural units constituting the water-soluble acrylic resin, Preferably, it is 10-80 mol%.

  The water-soluble acrylic resin contains ethylene, a linear α-olefin, a vinyl compound (I) other than structural units derived from α, β-unsaturated carboxylic acid and structural units derived from α, β-unsaturated carboxylic acid ester. ) And a structural unit derived from the addition-polymerizable monomer, the content is usually in a range where the adhesiveness of the resulting aqueous emulsion is not impaired, and a specific total The content is about 5 mol% or less, preferably 1 mol% or less, more preferably derived from addition-polymerizable monomers with respect to the structural units derived from all monomers constituting the water-soluble acrylic resin. The content is such that the structural unit is not substantially contained.

As the structural unit derived from the α, β-unsaturated carboxylic acid ester in the water-soluble acrylic resin, structural units derived from different types of α, β-unsaturated carboxylic acid esters may be used.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid esters obtained from an aliphatic alcohol having 1 to 20 carbon atoms and an α, β-unsaturated carboxylic acid The content of the derived structural unit is usually 5 to 95 mol%, preferably 10 to 80 mol% with respect to all the structural units constituting the water-soluble acrylic resin.
Among the structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated obtained from an α, β-unsaturated carboxylic acid and an aliphatic alcohol having 1 to 10 carbon atoms having an amino group Content of the structural unit derived from carboxylic acid ester is 0-80 mol% normally with respect to all the structural units which comprise a water-soluble acrylic resin, Preferably, it is 0-50 mol%.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated compounds obtained from α, β-unsaturated carboxylic acids and C 1-10 aliphatic alcohols having carboxylic acid groups Content of the structural unit derived from saturated carboxylic acid ester is 0-80 mol% normally with respect to all the structural units which comprise a water-soluble acrylic resin, Preferably, it is 0-40 mol%.
Among structural units derived from α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acids obtained from α, β-unsaturated carboxylic acids and C1-C10 aliphatic alcohols having a hydroxyl group A structural unit derived from an acid ester may be contained, and the content thereof is usually 0 to 50 mol%, preferably 1 to 30% with respect to all the structural units constituting the water-soluble acrylic resin. Mol%.

  As the water-soluble acrylic resin, the content of structural units derived from α, β-unsaturated carboxylic acid is 5 to 80 mol% and the number of carbon atoms is 1 with respect to all the structural units constituting the water-soluble acrylic resin. The structural unit content derived from the α, β-unsaturated carboxylic acid ester obtained from the aliphatic alcohol of ˜20 and the α, β-unsaturated carboxylic acid contains the structural unit of 10 to 80 mol%. It is preferable.

  As a method for producing a water-soluble acrylic resin, for example, a monomer (such as a monomer having a structural unit derived from an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid ester) is subjected to addition polymerization. The method of manufacturing by doing is mentioned. Specifically, alcohol such as isopropyl alcohol or water is used as a solvent, and a part or all of the monomer is mixed in the solvent, and the radical is usually at 0 to 50 ° C., preferably 0 to 30 ° C. The initiator and the remaining monomer are mixed, and usually stirred for about 1 to 24 hours. In order to control the reaction, a radical initiator may be added after dissolving in an organic solvent.

  Here, examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbohydrate). Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2- Azo compounds such as methyl propionate) and 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene Hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, tert Organic peroxides such as butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxidation such as potassium persulfate, ammonium persulfate, hydrogen peroxide Thing etc. are mentioned. A redox initiator using a thermal polymerization initiator and a reducing agent in combination can also be used as the polymerization initiator.

The aqueous emulsion of the present invention contains the above (A), (B) and (C). As a method for producing an aqueous emulsion, (A), (B) and (C) are melt-kneaded; the heating step (A) is heated, and the heated (A) obtained in the heating step is ( (B) a mixing step for mixing; a method including a kneading step for kneading (A) and (B), and a step for dispersing the kneaded product obtained in the kneading step in (C); ) In an organic solvent such as toluene, a mixing step in which the lysate obtained in the dissolving step is mixed with (B), and a removal in which the organic solvent is removed from the mixture obtained in the mixing step A method including a step; and the like.
Moreover, the emulsion manufacturing method by chemical emulsification methods, such as self-emulsification other than the above mechanical emulsification methods, is also illustrated.
A method comprising a kneading step of kneading (A) and (B) and a step of dispersing the kneaded product obtained in the kneading step in (C) is preferable. Among them, the kneading step is caused to act on shear stress. However, it is more preferable to carry out.

  Examples of the apparatus used in the step of melt kneading (A) and (B) and (C) as necessary include, for example, a twin screw extruder, Labo Plast Mill (Toyo Seiki Seisakusho), Labo Plast Mill Micro ( Toyo Seiki Seisakusho Co., Ltd.) and other multi-screw extruders, homogenizers, Equipment with a barrel (cylinder) such as K Fillmix (registered trademark of Primix Co., Ltd.), for example, stirring tank, chemical stirrer, vortex mixer, flow jet mixer, colloid mill, ultrasonic generator, high-pressure homogenizer, Mr. Dispersion ( Examples of such devices include a registered trademark of Fujikin Co., Ltd.), static mixers, micro mixers and the like that do not have a barrel (cylinder).

As a shear rate of the apparatus which has a barrel, it is about 200-100000 second- ¹ normally, Preferably it is about 1000-2500 second- ¹ . When the shear rate is 200 seconds ⁻¹ or more, the adhesiveness of the resulting emulsion tends to improve, and when it is 100,000 seconds ⁻¹ or less, production tends to be easy industrially. preferable.
Here, the shear rate is a numerical value obtained by dividing the peripheral speed [mm / sec] of the outermost peripheral part of the screw element by the clearance [mm] between the screw and the barrel.

As a method of melt kneading (A), (B) and (C), for example, (A) is continuously supplied from a hopper or a supply port of a twin-screw extruder, and this is heated and melt-kneaded. (B) is pressurized and supplied from at least one supply port provided in the compression zone, metering zone or degassing zone of the extruder, and (A) is kneaded with a screw, followed by compression of the extruder. Examples thereof include a method of continuously producing an aqueous emulsion from a die by supplying (C) from at least one supply port provided in the zone.
As a method including a heating step of heating (A) and a mixing step of mixing (B) with the heated (A) obtained in the heating step, for example, after heating a cylinder of a kneader, the cylinder (A) is charged into the inside, and a heating process is performed to melt while rotating. Next, (B) is added and a mixing process is performed to rotate. Subsequently, hot water is added to the resulting mixture to disperse. And a method of obtaining an aqueous emulsion.
A method using a multi-screw extruder is suitable as the method including the heating step of heating (A) and the mixing step of mixing (B) with the heated (A) obtained in the heating step.
Specifically, first, a heating step in which (A) is supplied from a hopper of a multi-screw extruder having two or more screws in a casing, and heated and melt-kneaded, then, a compression zone of the extruder or / And a method for producing the aqueous emulsion of the present invention through a mixing step of dispersing in (C) while kneading with (B) supplied from at least one liquid supply port provided in the measuring zone. .

The aqueous emulsion of the present invention is preferably one in which the dispersoid containing (A) and (B) is dispersed in (C) which is a dispersion medium.
The volume-based median diameter of the dispersoid is usually 0.01 to 3 μm, preferably 0.5 to 2.5 μm, more preferably 0.5 to 1.5 μm.
When the volume-based median diameter is 0.01 μm or more, it is preferable from the viewpoint of easy production, and when it is 3 μm or less, adhesiveness tends to be improved.
Here, the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis.

  Examples of the emulsion of the present invention include aqueous emulsions such as polyurethane aqueous emulsions and ethylene-vinyl acetate copolymer aqueous emulsions; thermosetting resins such as urea resins, melamine resins, and phenol resins; clays, kaolin, talc, and calcium carbonate. Preservatives; rust preventives; antifoaming agents; foaming agents; thickeners such as polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch; viscosity modifiers; flame retardants; titanium oxide Pigments such as dibasic acids such as dimethyl succinate and dimethyl adipate; plasticizers;

  The aqueous emulsion of the present invention is coated on the adherend layer as necessary, and then dried to give a cured product. Such an aqueous emulsion of the present invention can usually be used for paints, primers, base materials, adhesives, and the like, and a cured product obtained by drying this becomes a coating film or an adhesive layer. Such a cured product has excellent adhesiveness to an adherence layer of polyolefin such as polypropylene, which has been conventionally difficult to adhere.

  For example, wood, plywood, medium density fiberboard (MDF), particle board, fiber board and other woody materials; cotton, linen, rayon and other cellulosic materials; polyethylene (structural units derived from ethylene) Polyolefin (mainly a structural unit derived from propylene, the same applies hereinafter), polystyrene (polyolefin having a structural unit derived from styrene as a main component, the same applies hereinafter), etc. Plastic materials such as polyolefin, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane; ceramic materials such as glass and ceramics; iron, Stainless steel, copper Metallic material such as aluminum; and the like.

  Such an adhesion layer may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber or the like and a plastic material may be used.

  Here, the polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO). The urethane foam is a polyurethane foamed by a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water used as a crosslinking agent. Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.

  The adherent layer is preferably at least one material selected from the group consisting of wood-based materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. Among these materials, polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene are preferable. A polymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum, and polyurethane are preferable, and polypropylene, polyvinyl chloride, glass, aluminum, and polyurethane are more preferable.

  The laminate of the present invention has the above-mentioned adherent layer and a layer derived from the aqueous emulsion of the present invention. As a method for producing such a laminate, for example, a first step of applying the aqueous emulsion of the present invention to the above-described adherent layer to obtain a coated product having the adherent layer and a layer containing the aqueous emulsion; There is a production method including a second step of drying the coated product obtained in the first step to obtain a laminate having the adherent layer and a layer derived from an aqueous emulsion.

When one of the adherent layers is a water-absorbent adherent layer such as a wood-based material or a cellulose-based material, the aqueous emulsion of the present invention can be applied as it is and bonded to another adherent layer. That is, after an aqueous emulsion is applied to a water-absorbing layer, another layer (which may be water-absorbing or non-water-absorbing) is laminated on the layer derived from the aqueous emulsion. Moisture is absorbed by the water-absorbing adherent layer, and the layer derived from the aqueous emulsion becomes an adhesive layer, and a laminate having a water-absorbing adherent layer / cured product layer / adhesive layer can be obtained.
When both of the adherend layers are non-water-absorbing, after applying the aqueous emulsion of the present invention to one adherend on one side and drying to form a cured product layer derived from the aqueous emulsion, the other The adhering layer may be bonded and heated for adhesion.

  The present invention further provides a method for forming a coating film comprising the step of applying the aqueous emulsion of the present invention to the surface of the adherend layer and the use of the aqueous emulsion of the present invention for forming the coating film of the present invention. Such a method for forming a coating film may further include a drying step. Moreover, you may apply | coat a liquid material as a coating material further to the coating film obtained. As the coating material, a material exemplified as the material of the adherent layer such as polyurethane, and a liquid material is preferable because of excellent adhesion to the cured product.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified.
[Solid content]
The solid content was measured by a measuring method according to JIS K-6828.

[Particle size]
This is a volume-based median diameter obtained using a laser diffraction particle size distribution analyzer LA-910 (manufactured by HORIBA) at a particle refractive index of 1.50-0.20i.

<Example of production of water-soluble acrylic resin (B-1)>
The monomers listed in Table 1 were used as the monomers.

"AA" 7.5 parts (10.9 mole ratio), "MAA" 22.5 parts (27.4 mole ratio), "HEA" 29.5 parts (26.6 mole ratio), "EA" 29. 5 parts (30.8 molar ratio) and 11 parts of “SLMA” (4.4 molar ratio) were mixed at 10 to 30 ° C. to obtain 100 parts of a monomer mixture. Here, the molar ratio represents the number of moles when the total number of moles of the monomers is 100.
A reactor was charged with 150 parts of isopropyl alcohol (hereinafter sometimes referred to as IPA) and the monomer mixture, and the reactor was purged with nitrogen, followed by 0.9 part of 2,2′-azobisisobutyronitrile. Was stirred at 80 ° C. for 2 hours as a polymerization initiator. Subsequently, the temperature of the resulting reaction solution was raised to a boiling point to distill off the IPA, and after distilling, the internal temperature was lowered to 50 ° C., and then 29 parts (48 molar ratio) of 28% aqueous ammonia solution was mixed. Then, solid content was adjusted with water and the viscous water-soluble acrylic resin (B-1) was obtained (yield 90%).

<Example of production of water-soluble acrylic resin (B-1 ′)>
As the monomer (B-1 ′), the monomers listed in Table 1 were used.

"AA" 7.5 parts (10.5 molar ratio), "MAA" 22.5 parts (26.2 molar ratio), "MMA" 59 parts (59.1 molar ratio) and "SLMA" 11 parts (4 .2 molar ratio) was mixed at 10 to 30 ° C. to obtain 100 parts of a monomer mixture. Here, the molar ratio represents the number of moles when the total number of moles of the monomers is 100.
A reactor was charged with 150 parts of isopropyl alcohol (hereinafter sometimes referred to as IPA) and 100 parts of ion-exchanged water, and the internal temperature was adjusted to 80 ° C. while stirring. After the reaction vessel was purged with nitrogen, 20 parts of the monomer mixture was added all at once. Further, 2 parts of 2,2′-azobisisobutyronitrile was added as a polymerization initiator and stirred at the same temperature. Next, it stirred at the same temperature, dripping 80 parts of this monomer liquid mixture over 4 hours. Every 1 hour after the start of dropping of the monomer mixture, 0.15 parts of the polymerization initiator was added in four portions, and the mixture was further stirred for 3 hours at the same temperature. Subsequently, the temperature of the resulting reaction solution was raised to the boiling point to distill off the IPA. After distilling off, the internal temperature was lowered to 50 ° C., and then 26.5 parts (44 mole ratio) of 28% aqueous ammonia solution. After mixing, a viscous water-soluble acrylic resin (B-1 ′) was obtained (yield 90%, hereinafter referred to as (B-1 ′)).

  The emulsifiers obtained in each of the above production examples are summarized in Table 2.

Example 1: Production of Aqueous Emulsion (E-1) Irie Shokai Desk Type Kneader PBV-0.3 Type Acrylic Copolymer (A-1) BondFirst (registered trademark) CG5001 (manufactured by Sumitomo Chemical Co., Ltd., MFR: about 200 g / 10 minutes (190 ° C., hereinafter referred to as “bond first”) was charged in 100 parts, and the bond first was heated and melted at a screw rotation speed of 10 rpm for 7 minutes while maintaining at 97 ° C.
Subsequently, 10 parts (solid content) of the water-soluble acrylic resin (B-1) was supplied, and kneaded for 3 minutes at a rotation speed of the screw of 60 rpm while maintaining the temperature at 97 ° C., and 100 parts of ion-exchanged water at 90 ° C. By adding and dispersing, a milky white aqueous emulsion was obtained. The particle diameter of the obtained aqueous emulsion (E-1) was 1.40 μm.

Example 2 Production of Aqueous Emulsion (E-1 ′) Cylinder of Co-rotating Engagement Type Twin Screw Extruder (Technovel: KZW15TW-15 / 45MG-NH (−1100), L / D = 45) After setting the temperature to 110 ° C., from the hopper of the extruder, BondFirst (registered trademark) CG5001 (manufactured by Sumitomo Chemical Co., Ltd., MFR: about 200 g / 10 minutes (190 ° C), hereinafter Bond First) was continuously fed at a screw rotation speed of 500 rpm, and Bond Fast was heated.
10 parts (solid content) of a water-soluble acrylic resin (B-1 ′) is continuously supplied from a supply port provided in the vent part of the extruder while being pressurized with a gear pump, Bond First and (B-1 ′) Were mixed while being continuously extruded, and 100 parts of ion-exchanged water was added from a supply port provided in the vent part while being pressurized with a plunger pump to obtain a milky white aqueous emulsion. The particle diameter of the obtained aqueous emulsion (E-1 ′) was 0.70 μm.

Reference Example 1: Manufacture of aqueous emulsion (E-2) Irie Shokai Desk type kneader PBV-0.3 type with acrylic copolymer (A-1) BondFirst (registered trademark) CG5001 (manufactured by Sumitomo Chemical Co., Ltd., MFR: about 200 g / 10 minutes (190 ° C., hereinafter referred to as “bond first”) was charged in 100 parts, and the bond first was heated and melted at a screw rotation speed of 10 rpm for 7 minutes while maintaining at 97 ° C.
Subsequently, 10 parts of nonionic emulsifier (Pluronic (registered trademark) F-108, manufactured by ADEKA Corporation) and 10 parts of ion-exchanged water are supplied, and the mixture is kneaded for 4 minutes at a rotation speed of 60 rpm with the screw maintained at 97 ° C. Then, 100 parts of ion exchange water at 90 ° C. was added and dispersed to obtain a milky white aqueous emulsion. The particle diameter of the obtained aqueous emulsion (E-2) was 1.84 μm.

<Example of pigment paste production>
In a 200 mL container made of SUS for sand grinder, 53.4 g of Acreset (registered trademark) ARL-460 (solid content 50.8%, manufactured by Nippon Shokubai Co., Ltd.) and 1.2 g of Surfynol (registered trademark) 104 (solid content 50) 0.0%, manufactured by Shin-Etsu Chemical Co., Ltd.) and 85.1 g of ion-exchanged water were added, and the resulting mixture was stirred at 300 rpm for 10 minutes to obtain (Formulation 1).
Subsequently, (Formulation 1), 15.1 g of carbon black: MA-100 (manufactured by Mitsubishi Plastics), 30.1 g of talc: NK-64 (manufactured by Fuji Talc), and 15.1 g of titanium oxide: Typek R820 (manufactured by Ishihara Sangyo Co., Ltd.) was mixed, and the resulting mixture was stirred at 600 rpm for 30 minutes to obtain (Formulation 2).
Further, this (Compound 2) and 200 g of glass beads (1.0 mmφ) were mixed, and the resulting mixture was used in a 6-cylinder sand grinder (manufactured by Igarashi Kikai Co., Ltd.) in the range of 25-30 ° C. After stirring at 2000 rpm for 8 hours, the mixture was filtered through a 200-mesh filter cloth to obtain a pigment paste having a solid content of 45.5%.
The following tests were performed using the obtained pigment paste.

Test Example: Adhesive Evaluation While stirring 20.0 g of pigment paste with a three-one motor, there was a mixture of 3.9 g of an aqueous emulsion (E-1) in terms of solid content and 0.68 g of 20% urea water. Was added dropwise over 5 minutes, and after the addition, the mixture was further stirred for 5 minutes to prepare a test compound. Similarly, it replaced with the water-based emulsion (E-1), and created the compound for a test using (E-1 ') and (E-2), respectively. Each test compound obtained was evaluated for adhesion.
<Adhesiveness>
Each test compound is applied to a polypropylene substrate (adhesion layer) so that the film thickness is about 10 μm after drying, and heat treatment is performed at 120 ° C. for 30 minutes, resulting in an aqueous emulsion on the surface of the polypropylene substrate. The laminated body which has the layer to perform as a coating film was obtained. A cut of 100 squares with a width of 1 mm was made in the coating film, and the number of squares in which the coating film remained completely was counted by cellophane tape peeling. Adhesiveness was evaluated by the amount of the coating film remaining after peeling the cellophane tape three times. A larger number (closer to 100) means better adhesion. The results are shown in Table 3.

<Solvent resistance test>
(Example 3)
The aqueous emulsion (E-1) was cast into release PET and allowed to stand at 23 ° C. for 3 days to obtain a dry film. The obtained film was cut to a grain size of rice and heat-treated at 80 ° C. for 20 minutes. Then, toluene was added so that the concentration became 1%, and left for 16 hours. Thereafter, the mixture was filtered through a 300-mesh wire mesh, the filtration residue was heat-treated at 140 ° C. for 30 minutes, and the elution rate was determined from the change in weight. The smaller the number, the better the solvent resistance.
(Example 4)
It was 7.1% when the elution rate was calculated | required like (Example 3) except having used (E-1 ') instead of the aqueous emulsion (E-1).
(Reference Example 2)
It was 27.6% when the elution rate was calculated | required like (Example 3) except having used (E-2) instead of the water-based emulsion (E-1).
The results are shown in Table 4.

  Since the cured product derived from the aqueous emulsion of the present invention is excellent in adhesiveness to polypropylene, which has been conventionally considered to be difficult to adhere, the cured product derived from the aqueous emulsion of the present invention is conventionally regarded as difficult to adhere. It can be suitably used for an adherent layer of polyolefin such as polypropylene. Moreover, it is practically suitable also from being excellent in solvent resistance.

Claims (9)

An aqueous emulsion containing the following (A), (B) and (C).
(A) an acrylic copolymer containing a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester, and a structural unit derived from ethylene and / or a structural unit derived from propylene, or , A modified acrylic copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the copolymer , derived from the structural unit and / or methacrylic ester derived from the acrylic ester The structural unit is
X-OH
Wherein X is 1,2-epoxyethyl group, 1,2-epoxypropyl group, 1,2-epoxybutyl group, 1,2-epoxypentyl group, 1,2-epoxyhexyl group, 1,2- Represents an epoxyoctyl group or a 1,2-epoxydecyl group.)
A structural unit derived from an ester composed of an alcohol and acrylic acid and / or methacrylic acid, and a structural unit derived from the acrylic ester in the acrylic copolymer and / or a methacrylic ester. The content of the derived structural unit is 5 to 40% by weight with respect to all structural units constituting the acrylic copolymer, or an acrylic copolymer modified product (B ) An ionic emulsifier , wherein the ionic emulsifier is an anionic emulsifier, and the anionic emulsifier is converted into a structural unit derived from an α, β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid ester. A water-soluble acrylic resin containing a derived structural unit, wherein the α, β-unsaturated carboxylic acid ester is an aliphatic alcohol having 1 to 20 carbon atoms , Obtained from β- unsaturated carboxylic acid alpha, ionic emulsifiers (C) water is β- unsaturated carboxylic acid ester A method for producing an aqueous emulsion comprising a kneading step of kneading the following (A) and (B), and a step of dispersing the kneaded product obtained in the kneading step in the following (C).
(A) an acrylic copolymer containing a structural unit derived from an acrylate ester and / or a structural unit derived from a methacrylic acid ester, and a structural unit derived from ethylene and / or a structural unit derived from propylene, or , A modified acrylic copolymer obtained by graft polymerization of α, β-unsaturated carboxylic acids to the copolymer , derived from the structural unit and / or methacrylic ester derived from the acrylic ester The structural unit is
X-OH
Wherein X is 1,2-epoxyethyl group, 1,2-epoxypropyl group, 1,2-epoxybutyl group, 1,2-epoxypentyl group, 1,2-epoxyhexyl group, 1,2- Represents an epoxyoctyl group or a 1,2-epoxydecyl group.)
A structural unit derived from an ester composed of an alcohol and acrylic acid and / or methacrylic acid, and a structural unit derived from the acrylic ester in the acrylic copolymer and / or a methacrylic ester. The content of the derived structural unit is 5 to 40% by weight with respect to all structural units constituting the acrylic copolymer, or an acrylic copolymer modified product (B ) An ionic emulsifier , wherein the ionic emulsifier is an anionic emulsifier, and the anionic emulsifier is converted into a structural unit derived from an α, β-unsaturated carboxylic acid and an α, β-unsaturated carboxylic acid ester. A water-soluble acrylic resin containing a derived structural unit, wherein the α, β-unsaturated carboxylic acid ester is an aliphatic alcohol having 1 to 20 carbon atoms , Obtained from β- unsaturated carboxylic acid alpha, ionic emulsifiers (C) water is β- unsaturated carboxylic acid ester The production method according to claim 2 , wherein the kneading step of kneading (A) and (B) is carried out while applying a shear stress. Wood-based materials, cellulose-based materials, plastic materials, laminate having a deposited layer comprising at least one material selected from the group consisting of ceramic and metallic materials, and a layer derived from the aqueous emulsion of claim 1 Symbol placement body. The laminate according to claim 4 , wherein the adherend is a polyolefin. Wood-based materials, cellulose-based materials, plastics materials, the adherend composed of at least one material selected from the group consisting of ceramic and metallic materials, coating the aqueous emulsion according to claim 1 Symbol placement,該被wear A first step of obtaining a coated product having a layer and a layer containing the aqueous emulsion;
The manufacturing method of a laminated body characterized by including the 2nd process of drying the coated article obtained at the 1st process, and obtaining the laminated body which has the said adherence layer and the layer derived from an aqueous emulsion. Method of forming a coating film comprising the step of applying an aqueous emulsion of claim 1 Symbol placement on the deposition layer surface. Use of an aqueous emulsion of claim 1 Symbol placement for forming a coating film. A cured product obtained aqueous emulsion of claim 1 Symbol placement dried.